EP0696307B1 - Compositions d'adhesifs autocollants acryliques durcissables aux ultraviolets comprenant des monomeres fonctionnels carbamate et adhesifs prepares avec ces compositions - Google Patents

Compositions d'adhesifs autocollants acryliques durcissables aux ultraviolets comprenant des monomeres fonctionnels carbamate et adhesifs prepares avec ces compositions Download PDF

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Publication number
EP0696307B1
EP0696307B1 EP94914240A EP94914240A EP0696307B1 EP 0696307 B1 EP0696307 B1 EP 0696307B1 EP 94914240 A EP94914240 A EP 94914240A EP 94914240 A EP94914240 A EP 94914240A EP 0696307 B1 EP0696307 B1 EP 0696307B1
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Prior art keywords
weight
acrylate
parts
sensitive adhesive
pressure
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EP94914240A
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German (de)
English (en)
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EP0696307A1 (fr
Inventor
Martine H. Deketele
Yvan A. Bogaert
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3M Co
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Minnesota Mining and Manufacturing Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present invention relates to an acrylic pressure-sensitive adhesive composition having improved overall performance (higher adhesion and cohesive strength) by incorporating a carbamyloxy alkyl (meth)acrylate as a comonomer in the acrylic copolymer.
  • Acrylate pressure-sensitive adhesives are well known in the art.
  • alkyl acrylate copolymers which are predominantly alkyl esters of acrylic acid having from 4 to 14 carbon atoms and which further comprise a minor amount of a polar copolymerizable monomer such as acrylic acid.
  • Such adhesives are widely popular as they are readily available, and provide a good balance of tack, shear, and peel properties on a variety of substrates at a relatively low cost. Methods for making these adhesives involve the use of large amounts of solvent which is an effective method for polymerization of acrylate adhesives, but one which is increasingly object to safety and environmental restrictions.
  • U.S. Patent No. 4,292,231 discloses acrylic pressure-sensitive adhesives having improved cohesive strength.
  • the adhesive is formed by reaction of an acrylic terpolymer with a metal alkoxide or chelated metal alkoxide such as a chelated ester of orthotitanic acid.
  • a metal alkoxide or chelated metal alkoxide such as a chelated ester of orthotitanic acid.
  • Gabriel et al. is limited to monomers containing both carbamate and carboxylic acid functionality in a ratio of 1/1.
  • column 7, lines 16-21 Gabriel et al. state that "Example 11 was included to demonstrate that applicant's invention requires a monomer containing both a carbamate group and an acid group.
  • the adhesive as described by Gabriel et al. is made by solution polymerization.
  • column 4, lines 53-58 they state that "the polymer systems of this invention may also be prepared in mass or non-aqueous dispersion type polymerization processes as are well known to those skilled in the art. However, solution polymerization processes are preferred". The use of other polymerization techniques is not exemplified.
  • U.S. Patent No. 4,181,752 discloses a process for making pressure-sensitive adhesive tape which involves the ultraviolet photopolymerization of alkyl esters of acrylic acid and polar copolymerizable monomers to form the acrylate copolymer. Martens teaches that intensity and spectral distribution of the irradiation must be controlled in order to attain desirable cohesive strength and peel resistance.
  • the photopolymerization is preferably carried out in an inert atmosphere as oxygen tends to inhibit the reaction.
  • Benefits of ultraviolet-radiation polymerized adhesives include safety and environmental improvements due to the elimination of solvents in the processing.
  • a number of patents disclose the ultraviolet radiation polymerization of acrylate adhesives.
  • U.S. Patent No. 4,364,972 (Moon) discloses the use of N-vinylpyrrolidone as the polar copolymerizable monomer in the acrylate adhesive copolymer to provide a pressure-sensitive adhesive with high adhesion to automotive paints.
  • Acrylic pressure-sensitive adhesives generally have a good balance of tack, peel, and shear properties.
  • the tack property relates to the adhesive's ability to adhere quickly
  • the peel property relates to the adhesive's ability to resist removal by peeling
  • the shear property relates to the adhesive's ability to hold in position when shear forces are exerted.
  • the tack and peel properties are directly related to each other but are inversely related to the shear property.
  • an increase in adhesive properties is required.
  • the adhesive properties of an adhesive can be increased by using a tackifying resin. Typically, the addition of tackifying agents yields a 30% increase in adhesion.
  • the above-cited Moon patent which concerns pressure-sensitive adhesives designed specifically to provide enhanced adhesion to automotive paints, teaches that tackifiers can be blended into the photoactive mixtures of monomers from which those pressure-sensitive adhesives are photopolymerized, but warns, at column 6, lines 8-12, that "the addition of any such material adds complexity and hence expense to an otherwise simple, straight forward, economical process, and is not preferred, except to achieve specific results".
  • the Moon patent does not exemplify this teaching.
  • the introduction of a tackifier into a photopolymerizable mixture of monomers often interferes with the photopolymerization and prevents the attainment of the desired adhesive and cohesive properties.
  • U.S. Patent No. 4,988,742 discloses acrylic terpolymer pressure-sensitive adhesives comprising photopolymerized polymers containing an alkyl acrylate monomer, a first (strongly) polar copolymerizable monomer, a second (strongly or moderately) polar monomer, and a hydrogenated rosin ester tackifying agent.
  • the glass transition temperature of the adhesive as measured by dynamic mechanical thermal analysis (DMTA) is lower than for an identical acrylic terpolymer omitting the tackifying agent.
  • U.S. Patent No. 5,028,484 discloses a pressure-sensitive adhesive comprising ultraviolet polymerized acrylic polymer and tackifying resins.
  • the tackifying resins are aromatic polymeric resins which have an average molecular weight of 300 to 2,500, a polydispersity index of less than 5, a glass transition temperature of 40° to 120°C and a solubility parameter of 7 to 9.5 (cal/cc)-1 ⁇ 2
  • the adhesive has a monomer conversion factor of at least 98%.
  • the tackified pressure-sensitive adhesive of the invention has good storage stability, i.e., said pressure-sensitive adhesive loses no more than 30% (the claims and abstract refer to about 70%; the specification about 30%) of its adhesion when aged for a period of two weeks at 70°C.
  • Applicants have found such an adhesive. Applicants have now discovered that the use of from 5 to 45 parts of a carbamyloxyalkyl (meth)acrylate as a comonomer in an acrylic adhesive formulation results upon cure in a pressure-sensitive adhesive having increased adhesion, comparable to a conventional tackified acrylic pressure-sensitive adhesive, and at the same time demonstrating an increase in cohesive strength.
  • the pressure-sensitive adhesive of the invention also displays good storage stability.
  • the present invention provides a pressure-sensitive adhesive having high adhesion properties and at the same time high cohesive strength, comprising an ultraviolet radiation polymerized copolymer comprising:
  • the invention also relates to pressure-sensitive adhesive compositions from which the pressure-sensitive adhesive of the invention is formed.
  • the pressure-sensitive adhesive composition comprises:
  • the pressure-sensitive adhesive composition preferably possesses a viscosity of 500 mPa ⁇ s (cps) to 10,000 mPa ⁇ s (cps).
  • the pressure-sensitive adhesive composition typically would possess a viscosity of 500 mPa ⁇ s (cps) to 10,000 mPa ⁇ s (cps) by virtue of one or both of the following: (i) prepolymerization of one or more of the monomers of elements (a), (b), (c) and (d); or (ii) the addition of a thickening agent to said pressure-sensitive adhesive composition.
  • the invention also relates to substrates coated with the pressure-sensitive adhesive of the invention.
  • the pressure-sensitive adhesive of the invention will be in the form of a thin layer carried by a substrate to which it may be either permanently or temporarily adhered.
  • the resultant product is a normally tacky pressure-sensitive adhesive tape.
  • the substrate is provided with a release coating, on which the pressure-sensitive adhesive is coated, the pressure-sensitive adhesive is temporarily adhered in the form of a so-called transfer tape.
  • the acrylic copolymer pressure-sensitive adhesives of the present invention comprise an alkyl acrylate monomer, an acrylic monomer comprising carbamate functionality, and at least one polar copolymerizable monomer.
  • Useful alkyl acrylate monomers are the monofunctional unsaturated acrylate esters of non-tertiary noncyclic alkyl alcohols, the non-tertiary alcohols of which comprise from 4 to 14 carbon atoms.
  • Such non-polar monomers include, but are not limited to those selected from the group consisting of isooctyl acrylate, 2-ethyl hexyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate, butyl acrylate, hexyl acrylate, and mixtures thereof.
  • Preferred non-polar alkyl acrylate monomers include those selected from the group consisting of isooctyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.
  • the acrylic copolymer of the invention comprises from 50 to 94 parts by weight of the alkyl acrylate monomer, more preferably from 55 to 70 parts by weight, based upon 100 parts by weight total monomer in the copolymer.
  • the polymerizable composition further comprises an acrylic monomer containing carbamate functionality, which is copolymerizable with the alkyl acrylate monomer and polar monomer.
  • Useful monomers contain one carbamate functional group.
  • the synthesis of acrylic monomers having carbamate functionality is disclosed in U.S. Patent Nos. 3,674,838 (Nordstrom), 4,126,747 (Cowherd III et al.) and 4,279,833 (Culbertson et al.).
  • the carbamyloxyalkyl (meth)acrylate monomers useful in the present invention are illustrated by the following formula: wherein R 1 is selected from the group consisting of -H and CH 3 , R 2 is a divalent hydrocarbon radical comprising 1 to 12 carbon atoms, and R 3 is selected from the group consisting of lower alkyl radicals comprising 1 to 8 carbon atoms and hydrogen.
  • Divalent hydrocarbon radicals include but are not limited to those selected from the group consisting of divalent alkylene radicals including but not limited to those selected from the group consisting of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, dodecamethylene, among others.
  • Examples of useful carbamyloxyalkyl (meth)acrylate monomers include but are not limited to those selected from the group consisting of N-methylcarbamyloxymethyl (meth)acrylate, N-ethylcarbamyloxymethyl (meth)acrylate, N-methyl-2-carbamyloxyethyl (meth)acrylate, N-ethyl-2-carbamyloxyethyl (meth)acrylate, N-t-butyl-2-carbamyloxyethyl (meth)acrylate, N-ethyl-4-carbamyloxybutyl (meth)acrylate, N-methyl-4-carbamyloxybutyl (meth)acrylate, and mixtures thereof.
  • the acrylic copolymer of the invention comprises 5 to 45 parts by weight, preferably from 10 parts to 35 parts by weight, e.g 10 parts to 25 parts, for performance and cost reasons, of acrylic monomer containing carbamate functionality based upon 100 parts by weight total monomer contained in the ultraviolet radiation polymerized copolymer.
  • the polar monomer which is copolymerizable with the alkyl acrylate monomer and the carbamyloxyalkyl (meth)acrylate monomer can be selected from the group consisting of strongly polar copolymerizable monomers including but not limited to those selected from the group consisting of acrylic acid, itaconic acid, hydroxyalkyl acrylates, acrylamides, substituted acrylamides and mixtures thereof, and/or from moderately polar copolymerizable monomers including but not limited to those selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, N,N-dimethylacrylamide and mixtures thereof.
  • the copolymer of the invention comprises 1 to 15 parts by weight, preferably 5 to 10 parts by weight for performance reasons, strongly polar copolymerizable monomer based upon 100 parts by weight total monomer contained in the ultraviolet radiation polymerized copolymer and/or the copolymer of the invention comprises 1 to 35 parts by weight, preferably 15 to 30 parts by weight for performance reasons, moderately polar copolymerizable monomer based upon 100 parts by weight total monomer contained in the ultraviolet radiation polymerized copolymer.
  • the adhesive composition of the invention comprises a photoinitiator to induce polymerization of the monomers.
  • Photoinitiators which are useful include but are not limited to those selected from the group consisting of the benzoin ethers such as benzoin methyl ether and benzoin isopropylether, substituted benzoin ethers such as anisole methyl ether, substituted acetophenones such as 2,2-dimethoxy-2-phenyl acetophenone, substituted alpha-ketols such as 2-methyl-2-hydroxy propiophenone, aromatic sulfonyl chlorides such as 2-naphtalene sulfonyl chloride, and photoactive oximes such as 1-phenyl-1,1-propanedione-2-ethoxycarbonyl-oxime, and mixtures thereof.
  • the photoinitiator is typically present in an amount of 0.01 percent to 1 percent by weight based on the total weight of the monomer in the adhesive of the invention (polar monomer,
  • the adhesive composition of the invention may optionally further comprise a crosslinking agent.
  • Preferred crosslinking agents for acrylic pressure-sensitive adhesives are multiacrylates such as 1,6-hexanediol diacrylate as well as those disclosed in U.S. Patent No. 4,379,201 (Heilman et al.).
  • Other types of crosslinking agents are also useful, e.g., any of the triazine crosslinking agents taught in U.S. Patent Nos. 4,330,590 (Vesley) and 4,329,384 (Vesley et al.).
  • the crosslinking agent is typically used in the range of from 0.01 to 1 percent by weight based on the total weight of monomer in the adhesive of the invention (polar monomer, alkyl acrylate monomer, plus carbamate functional monomer).
  • the adhesive of the invention may be coated on at least one side of a substrate such as a backing to form an adhesive tape.
  • the adhesive may be adhered to a variety of substrates.
  • a laminated foam tape may be prepared by coating the adhesive of the invention on one side of a core layer. The opposite side of the core layer is bonded to a backing layer, optionally with adhesive which may be the adhesive of the invention to form a laminated foam tape.
  • the adhesive of the invention can be coated on a release liner to form an adhesive transfer tape.
  • the release liner typically comprises a backing coated with a release material such as those well known in the art (i.e. silicone).
  • the tapes of the invention can have a backing and/or core layer.
  • U.S. Patent No. 5,079,067 describes useful backing and core layers.
  • the core layer may consist of such materials as acrylates, polyethylenes, polypropylenes, neoprenes, polyolefins, polyurethanes, silicones, etc.
  • the core layer may be a foam-like layer, e.g., a monomer blend comprising microspheres may be used.
  • the microspheres may be glass or polymeric.
  • the microspheres should have an average diameter of 10 to 200 micrometers, and comprise from 5 to 65 volume percent of the core layer.
  • the thickness of the foam-like layers in preferred tapes of the invention range from 0.3 mm to 4.0 mm in thickness.
  • Preferred glass microspheres have average diameters of about 80 micrometers.
  • the polymeric matrix should be at least 3 times as thick as their diameter, preferably at least 7 times.
  • the thickness of the layers containing such glass microspheres should be at least six times, preferably at least twenty times that of each microsphere-free layer.
  • the backing may comprise a variety of materials including but not limited to those selected from the group consisting of cellulose acetate, polyvinylchloride, paper, polyethylene, polypropylene, and polyester.
  • the pressure-sensitive adhesive layer further comprises from about 2 to about 15 parts by weight of a hydrophobic silica having a surface area of at least 10 m 2 /g per 100 parts by weight of the pressure-sensitive adhesive copolymer.
  • the pressure-sensitive adhesive composition of the present invention can be prepared by premixing together the photopolymerizable non-polar alkyl acrylate monomer(s) and polar monomer(s) and a photoinitiator or thermal initiator. Examples of useful photoinitiators have been discussed previously.
  • thermal initiators include but are not limited to those selected from the group consisting of azo compounds such as 2,2-azobisisobutyronitrile, dimethyl 2,2'-azobis-isobutyrate, azobis-(diphenyl methane), 4,4-azobis-(4-cyanopentanoic acid); peroxides such as benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, glutaric acid peroxide, lauroyl peroxide; hydrogen peroxide, hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; peracids such as peracetic acid and perbenzoic acid; potassium persulfate; and peresters such as diisopropyl percarbonate.
  • azo compounds such as 2,2-azobisisobutyronitrile, dimethyl 2,2'-azobis-isobutyrate, azobis-(diphenyl me
  • This premix is then partially polymerized to an absolute viscosity in the range of from 500 mPa ⁇ s (cps) to 10,000 mPa ⁇ s (cps) to achieve a coatable syrup comprising prepolymer and unpolymerized monomers.
  • the acrylic carbamate is then dissolved in this syrup.
  • the acrylic carbamate monomer can be included in the premix along with the alkyl acrylate and polar monomer from which the syrup is made.
  • all the monomers (alkyl acrylate, acrylic carbamate, and polar) may be mixed with a sufficient amount of thixotropic agent such as fumed hydrophilic silica to achieve a syrup of coatable thickness (500 to 10,000 mPa ⁇ s (cps)) without a prepolymerization reaction.
  • thixotropic agent such as fumed hydrophilic silica
  • Photoinitiator is added to both types of syrup prior to polymerization to the copolymer of the invention.
  • Optional photocrosslinking agent and other useful materials as mentioned above may also be dissolved into either of these syrups.
  • This syrup (i.e., adhesive composition of the invention) is coated onto a flexible carrier web and polymerized in an inert, i.e., oxygen free, atmosphere, e.g., a nitrogen atmosphere.
  • an inert atmosphere i.e., oxygen free, atmosphere, e.g., a nitrogen atmosphere.
  • a sufficiently inert atmosphere can be achieved by covering a layer of the photoactive coating with a plastic film which is substantially transparent to ultraviolet radiation, and irradiating through that film in air as described in U.S. Patent No. 4,181,752 (Martens et al.).
  • the permissible oxygen content of the inert atmosphere can be increased by mixing into the polymerizable monomer an oxidizable tin compound as taught in U.S. Patent No. 4,303,485 (Levens), which also teaches that such procedures will allow thick coatings to be polymerized in air.
  • a preferred method of construction is multilayer coating, as described in U.S. Patent No. 4,818,610 (Zimmerman et al.), wherein a plurality of copolymerizable coatable compositions is prepared, each composition containing at least one photopolymerizable monomer, one of the coatable compositions being the novel pressure-sensitive adhesive of the invention.
  • the coatable compositions are coated to provide a plurality of superimposed layers with contiguous layers defining an interface there between, with the novel pressure-sensitive adhesive copolymer of the invention being coated as a first or last layer. Migration of photopolymerizable monomers through the interface between contiguous layers is permitted, and the superimposed layers are then simultaneously irradiated.
  • This provides polymeric chains comprised of copolymers of photopolymerizable monomers originating from contiguous layers extending through the interface there between, thereby producing a tape having layers which cannot be delaminated.
  • a tape test specimen 1.27 cm wide and about 15.2 cm long was secured by one of its ends to the test panel. The other end of the tape was held up to keep the sample loosely positioned over the test panel.
  • the tape was mechanically rolled down with one pass of a 2 kg roller at 30.5 cm/min. The free end of the tape was clamped into the jaw of a peel tester and the tape was pulled back at 180° at a rate of 30.5 cm/min. The tester records the average peel force in N/dm.
  • a mixture of IOA/AA 93.5/6.5 was partially thermally polymerized by using 0.016 part by weight of benzoylperoxide as an initiator based upon 100 parts by weight of IOA plus AA.
  • the partial polymerization was accomplished in an inert atmosphere (nitrogen) to provide a coatable syrup having an absolute viscosity of 500-10,000 mPa ⁇ s (cps).
  • Different amounts of N-butyl-2-carbamyloxyethyl acrylate available as Acticryl® CL1039 from SNPE, France
  • Comparative Example C-1 was made without the addition of Acticryl® CL1039 (also referred to herein as "CL1039").
  • Examples 15-17 were made from monomer mixtures containing IOA, AA and Acticryl® CL1039 in the ratios as given in Table 4. To each monomer mixture was added 0.15 part by weight IrgacureTM 651 initiator based upon the total weight of monomer. The samples were degassed and prepolymerized under UV light to obtain a syrup with a coatable viscosity.
  • Example 18 was made by UV prepolymerizing a mixture of IOA/AA 93.5/6.5 using 0.15 part by weight IrgacureTM 651 initiator. To this mixture were added amounts of AA and CL1039 to obtain a ratio of IOA/AA/CL1039 73.5/6.5/20. Comparative Example C-3 was made by UV prepolymerizing a mixture of IOA/AA 93.5/6.5 (using 0.15 part by weight IrgacureTM 651).
  • the results of this test indicate that high performance adhesives are made using the Acticryl® CL1039 comonomer independent of the way the prepolymerized syrup is made.
  • the prepolymer syrups can be made either thermally or by using UV light; the Acticryl® CL1039 can be added to a prepolymerized IOA/AA syrup or to the monomer mixture before prepolymerization.
  • a mixture of IOA/NVP 71/29 was partially thermally polymerized by using 0.016 part by weight of benzoylperoxide as an initiator based upon 100 parts by weight of IOA plus NVP.
  • the partial polymerization was accomplished in an inert atmosphere (nitrogen) to provide a coatable syrup having a viscosity of 500-10,000 mPa ⁇ s (cps).
  • 10 parts of Acticryl® CL1039 were added to the syrup, based upon 90 parts of syrup.
  • 0.3 part of IrgacureTM 651 based upon 100 parts by weight of the Acticryl® containing syrup and 0.15 part of HDDA based upon 100 parts by weight of the Acticryl® CL1039 containing syrup were added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Adhésif autocollant photopolymérisé qui adhère puissamment sur toutes les surfaces classiques et résiste étonnamment au cisaillement, comprenant le produit de réaction de la photopolymérisation d'un mélange constitué d'environ 50 à environ 94 parties en poids d'un ester d'acide acrylique d'un alcool d'alkyle non tertiaire contenant 4 à 14 atomes de carbone, environ 5 à environ 45 parties en poids d'un (méth)acrylate de carbamyloxyalkyle; environ 1 à environ 35 parties en poids d'un monomère copolymérisable polaire non saturé de monoéthylène, et environ 0,1 à environ 1 partie en poids de photoinitiateur.

Claims (10)

  1. Adhésif sensible à la pression comprenant un copolymère polymérisé par le rayonnement ultraviolet comprenant :
    (a) 50 à 94 parties en poids d'un ester d'acide acrylique d'un alcool alkylique non cyclique non tertiaire comprenant 4 à 14 atomes de carbone ;
    (b) 5 à 45 parties en poids d'un (méth)acrylate de carbamyloxyalkyle ;
    (c) éventuellement 1 à 15 parties en poids d'un monomère fortement polaire copolymérisable avec les monomères des éléments (a) et (b) et (d) ; et
    (d) éventuellement 1 à 35 parties en poids d'un monomère modérément polaire copolymérisable avec les monomères des éléments (a) et (b) et (c) ;
       où (a) plus (b) plus (c) plus (d) représentent un total de 100 parties en poids ; et où il faut que ledit copolymère comprenne du monomère polaire de l'élément (c), ou l'élément (d), ou les deux éléments (c) et (d).
  2. Adhésif sensible à la pression selon la revendication 1 qui comprend 10 à 35 parties en poids dudit (méth)acrylate de carbamyloxyalkyle.
  3. Adhésif sensible à la pression selon la revendication 1, où ledit (méth)acrylate de carbamyloxyalkyle est l'acrylate de N-butyl-2-carbamyloxyéthyle.
  4. Adhésif sensible à la pression selon la revendication 1, où ledit monomère fortement polaire est choisi dans le groupe constitué de l'acide acrylique, l'acide itaconique, les acrylates d'hydroxyalkyle, les acrylamides, les acrylamides substitués, et leurs mélanges.
  5. Adhésif sensible à la pression selon la revendication 1, où ledit monomère modérément polaire est choisi dans le groupe constitué de la N-vinylpyrrolidone, du N-vinylcaprolactame, de l'acrylonitrile, du N,N-diméthylacrylamide, et de leurs mélanges.
  6. Adhésif sensible à la pression selon la revendication 1, qui comprend en outre un agent de réticulation, où ledit agent de réticulation est présent en une quantité de 0,01 à 1% en poids par rapport au poids total de (a) plus (b) plus (c) plus (d).
  7. Adhésif sensible à la pression selon la revendication 1, où ledit monomère acrylate d'alkyle est choisi dans le groupe constitué des acrylate d'isooctyle, acrylate de 2-éthylhexyle, acrylate d'isononyle, acrylate de décyle, acrylate de dodécyle, acrylate de butyle, acrylate d'hexyle, et leurs mélanges.
  8. Adhésif sensible à la pression selon la revendication 1, où ledit adhésif comprend en outre des microsphères, où lesdites microsphères représentent 5 à 65% en volume de l'adhésif, où lesdites microsphères ont un diamètre moyen de 10 à 200 micromètres.
  9. Ruban adhésif sensible à la pression comprenant un support ayant l'adhésif sensible à la pression selon la revendication 1 qui adhère sur au moins une ses surfaces.
  10. Composition d'adhésif sensible à la pression comprenant :
    (a) 50 à 94 parties en poids d'un ester d'acide acrylique d'un alcool alkylique non cyclique non tertiaire comprenant 4 à 14 atomes de carbone ;
    (b) 5 à 45 parties en poids d'un (méth)acrylate de carbamyloxyalkyle ;
    (c) éventuellement 1 à 15 parties en poids d'un monomère fortement polaire copolymérisable avec les monomères des éléments (a) et (b) et (d) ; et
    (d) éventuellement 1 à 35 parties en poids d'un monomère modérément polaire copolymérisable avec les monomères des éléments (a) et (b) et (c ) ;
       où (a) plus (b) plus (c) plus (d) représentent un total de 100 parties en poids ; et où il faut que ladite composition comprenne du monomère polaire de l'élément (c), ou l'élément (d), ou les deux éléments (c) et (d) ;
       (e) 0,01 à 1% en poids d'un photoinitiateur par rapport au poids total de (a) plus (b) plus (c) plus (d).
EP94914240A 1993-04-30 1994-04-22 Compositions d'adhesifs autocollants acryliques durcissables aux ultraviolets comprenant des monomeres fonctionnels carbamate et adhesifs prepares avec ces compositions Expired - Lifetime EP0696307B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US5581993A 1993-04-30 1993-04-30
US55819 1993-04-30
PCT/US1994/004477 WO1994025537A1 (fr) 1993-04-30 1994-04-22 Compositions d'adhesifs autocollants acryliques durcissables aux ultraviolets comprenant des monomeres fonctionnels carbamate et adhesifs prepares avec ces compositions

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EP0696307A1 EP0696307A1 (fr) 1996-02-14
EP0696307B1 true EP0696307B1 (fr) 1997-11-05

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EP (1) EP0696307B1 (fr)
JP (1) JP3444423B2 (fr)
KR (1) KR960701966A (fr)
AU (1) AU6639294A (fr)
CA (1) CA2159721A1 (fr)
DE (1) DE69406658T2 (fr)
ES (1) ES2110746T3 (fr)
WO (1) WO1994025537A1 (fr)

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MXPA05006073A (es) 2002-12-12 2005-12-14 Surface Specialties Sa Proceso para producir (met)acrilatos de carbamoiloxi y nuevos (met)acrilatos de carbamoiloxi.
DE102005033622A1 (de) * 2005-07-19 2007-01-25 Basf Coatings Ag Laterale Carbamatgruppen und mit aktinischer Strahlung aktivierbare Gruppen enthaltende Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
US8821841B2 (en) 2005-08-11 2014-09-02 Basf Se Copolymers for cosmetic applications
WO2015038254A2 (fr) * 2013-08-06 2015-03-19 E. I. Du Pont De Nemours And Company Encres aqueuses pour l'impression à jet d'encre contenant des liants polymères avec des composants permettant l'interaction avec la cellulose
CN111056976A (zh) * 2019-12-31 2020-04-24 海聚高分子材料科技（广州）有限公司 一种氨基甲酸酯多（甲基）丙烯酸酯及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
US4111769A (en) * 1977-12-29 1978-09-05 Union Carbide Corporation Radiation curable pressure sensitive adhesive composition
JPS62167378A (ja) * 1986-01-21 1987-07-23 Toyo Ink Mfg Co Ltd 電子線硬化型感圧接着剤組成物
US4988742A (en) * 1988-09-02 1991-01-29 Minnesota Mining And Manufacturing Company Tackified terpolymer adhesives

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Publication number Publication date
EP0696307A1 (fr) 1996-02-14
DE69406658D1 (de) 1997-12-11
ES2110746T3 (es) 1998-02-16
JPH08509770A (ja) 1996-10-15
AU6639294A (en) 1994-11-21
DE69406658T2 (de) 1998-03-05
KR960701966A (ko) 1996-03-28
CA2159721A1 (fr) 1994-11-10
WO1994025537A1 (fr) 1994-11-10
JP3444423B2 (ja) 2003-09-08

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